A silver halide color photographic light-sensitive material (hereinafter sometimes referred to as a light-sensitive material or a photographic material), after exposed to light, is then processed in the steps such as a series of developing, desilvering, washing and stabilizing steps. And, a silver halide black-and-white photographic light-sensitive material, after exposed to light, is then processed in the series of developing and fixing steps. In these processes, a black-and-white developer or a color developer for carrying out a developing step, a bleacher or a bleach-fixer for a desilvering step, city water or deionized water for a washing step, a stabilizer for a non-water washing step, and a stabilizer for a dye-stabilizing step, respectively.
A liquid having a processing function for carrying out each of the above-mentioned processing steps is referred to as a processing solution. Each of the processing solutions is usually controlled to be a temperature within the range of 30.degree. to 40.degree. C., and a light-sensitive material is dipped in these processing solutions in order, so that it can be processed.
Such a process as mentioned above is commonly carried out by transporting a light-sensitive material, by making use of an automatic processor, through the respective processing tanks containing the above-mentioned processing solutions in order.
The term, "an automatic processor", stated herein generally means a processing machine having a developing unit, a fixing unit, a desilvering unit, a washing or stabilizing unit and a drying unit and also a means for automatically transporting a photographic light-sensitive material in order through each of the processing tank units.
When processing a light-sensitive material by making use of such an automatic processor as mentioned above, it has been popular to use a system for replenishing a processing chemical, for the purpose of keeping constant the activity of a processing solution contained in a processing tank.
As for the above-mentioned processing chemical replenishing systems, a system for making ready in advance a replenishing solution prepared by dissolving a processing chemical therein has widely been used.
To be more concrete, the processing operations have been carried out by timely supplying a replenishing solution prepared in advance from a replenishing solution tank to a processing tank.
In this case, a replenishing solution itself to be reserved in a replenishing tank is usually prepared at a separate place. In mini-labs and so forth, however, it has been common to prepare a specific amount of a replenishing solution at a time in a replenishing tank arranged closely to a processing machine. When preparing the replenishing solution, a dissolving work by hand or a dissolving-mixing work by a mixer has been carried out.
A processing chemical for silver halide photographic light-sensitive material use (hereinafter sometimes referred to as a photographic processing chemical) is available on the market in the powder or liquid form. When making use of the powder-formed, the solution thereof is prepared by dissolving it in a specific amount of water by hand. When making use of the liquid-formed, the solution thereof is prepared and then used upon lightly stirring and then diluting it with a specific amount of water, because the liquid was already concentrated.
There are some instances where a replenishing tank is arranged by the side of an automatic processor and, in this case, it is required to secure a considerably wide space. In the recently increasing minilabs, replenishing tanks are incorporated into the main body of an automatic processor. However, the replenishing tanks for 5- to 10-liter solutions are at least required, so that a space enough for these replenishing tanks is to be secured.
For displaying excellent and stable characteristics in a photographic process, a processing chemical for replenishment is separated into some parts. A color developing solution for color light-sensitive material is separated into 3 to 4 parts. The replenishing solution for a bleach-fixing for color light-sensitive material is separated into two parts, namely, a part of a ferric organic acid salt as an oxidizing agent and the other part of thiosulfuric acid as a reducing agent. When preparing the replenishing solution, a part of the above-mentioned ferric organic acid salt that was concentrated and the other part containing the thiosulfuric acid salt that was concentrated are mixed up together and a specific amount of water is then added thereto, so that the resulting replenishing solution may be used.
The resulting concentrated parts are available on the market in such a form that each part is put in a container such as those made of plastics and the containers are collectively put in an outer carton (such as a corrugated cardboard box) as a unit.
A processing chemical for replenishment comprising each kit of the above-mentioned parts is dissolved, diluted, mixed and then finished to be a specific amount, so that it may be used. However, these processing chemicals for replenishment have the following disadvantages.
The first disadvantage is as follows. Most of the conventional kits are in the form of a concentrated aqueous solution so concentrated as to improve the workability, that is seriously dangerous because the kits have a pH of not higher than 2.0 or not lower than 12.0. Accordingly, most of the kits are harmful to human body such as the adhesion thereof to human skin, and most of them are a strong oxidizing agent or reducing agent. Therefore, they have a seriously dangerous corrosive property particularly when they are transported by a boat or airplane. Also because they are in the form of an aqueous solution, the solubility thereof is limitative and they become heavier in weight and larger in volume than in the case of a solid form. Because such a concentrate as mentioned above is hazardous, it is required that the containers thereof will not be destroyed and the solution therein will not be spilt even when dropping them from a certain height. Therefore, the containers thereof are so made as to be more stronger, so that the disposal thereof has raised a problem.
The second disadvantage is as follows. Each part is put in an individual container and, when some processing chemical for replenishment is separately put in several part containers. In the case of a unit, the number of containers are considerably increased. Therefore, a wide space is required, especially when storing or transporting the units. For example, a color developer replenisher, CPK-2-20QA, that is a color paper processing solution is taken as a unit of 10 liters-, and it is separated into 3 parts, namely, a preservative-containing kit as Part A, a color developing agent-containing kit as Part B and an alkali as Part C, respectively. Parts A, B and C are each put in a 500 ml-capacity plastic container. Similarly, a bleach-fixer solution is taken as a unit of 8 liters, and the parts thereof are separately put in two bottles. These replenishers are put in variously sized outer cartons and are then stored or transported, respectively. However, a stabilizer is put in a relatively smaller outer carton having a size of about 17 cm.times.14 cm.times.16.5 cm and a bleach-fixer is put in a relatively larger outer carton having a size of about 18.5 cm.times.30.5 cm.times.22.5 cm. Therefore, only the same kind of a replenishers can be stored, transported or piled up in a shop and, resultingly, a large amount of space is required.
The third disadvantage is as follows. The disposal of an empty container is made problematic. Mainly in Europe and the U.S. in recent years, the protection of environment and the saving of resources have seriously been demanded. For the photographic industry, the disposal of a plastic container has particularly raised a problem. The plastic containers for photographic use are inexpensive in cost, convenient in storage and transportation and excellent in chemical resistance, however, they have almost no biodegradation property so that they may be piled up. When they are thrown into fire, a large amount of carbonic acid gas is produced to be a cause of warming the earth and falling acid rain. As for the problems for users, it is pointed out that a large number of plastic containers are piled up in a small working space and that the containers cannot be crushed out because they are hard, so that the space requirement may be made smaller.
The 4th disadvantage is that the chemicals used are extremely unstable.
The lifetime of a replenishing solution is usually two weeks even when a floating cover is used. Recently, however, the replenished amount of each processing solution has been reduced. For example, at a minilab receiving daily orders for average 30 rolls of color films and processing them, 10 liters of each replenishing solution is often used for not shorter than one month.
In such a case as mentioned above, each replenishing solution in replenishing tanks has much more opportunities to be exposed to the air than in the case of each processing solution in processing tanks, so that the replenishing solutions are deteriorated and, therefore, it has very often occurred to be quite non-sense even if any replenishments have been made. Accordingly, there have been devised to make a replenishing tank smaller to have a capacity of 5 liters or to make a replenishing kit smaller to have a reception capacity unit of 5 liters. In this case, a disadvantage is induced by that an additional packaging material is further required.
Besides the above, when taking an example of a replenishing solution for developing color paper, the replenishing solution for developing color paper is prepared in the following manner. After putting a given amount of water in a replenishing tank, a preservative-containing concentrated kit A is put therein and stirred up. Then, a color developing agent-containing concentrated kit B is put therein and stirred up. Finally, water is so added thereto as to make a given amount. In this case, some problems are liable to raise. For example, if a stirring is not satisfactory or if an initial water is forgotten to be added, the crystals of the color developing agent are liable to be deposited and a bellows pump is clogged with the resulting deposits thereof so as not to replenish the replenishing solution and, therefore, the photographic characteristics may be made sometimes unstable and the bellows pump may also be damaged. The concentrated kits are not always used immediately after preparing them, but they may be used one year or so after preparing them. In some case, the color developing agent and preservative may be oxidized so that the characteristics may become unstable.
It has been known that some additional problems are raised in a replenishing solution for color developing use contained in a replenishing tank. For example, when a replenishing solution is not used for a long time, some crystals may be made adhered to the walls of the replenishing tank and the replenishing solution may be liable to be oxidized and, further, tar and so forth may be produced. According to the preservation conditions, there raises such a problem that a component liable to be crystallized such as a color developing agent is deposited at a low temperature. It is, therefore, an actual situation that some manufacturers designate the specific preservation conditions for their replenishing solutions so that the users can control the conditions.
As described above, even when taking an example of a method in which a replenishing solution is prepared by making use of a commonly applicable concentrated kits or by making use of a powdered chemical, there is such a problem as mentioned above, and there also raises a similar problem in a bleach-fixing solution, a bleaching solution and a fixing solution. For example, a bleach-fixing solution has a seriously low grade characteristics in preservability. Because a bleach-fixing treatment is carried out immediately after treating with a high pH color developing solution. The alkaline color fixing solution is commonly carried in by a sheet of paper subject to treatment. It is, therefore, usual that an acidity is made higher and a pH is made substantially lower for neutralizing the color fixing solution. When making use of a low-pH bleach-fixing solution comprising a thiosulfate and an oxidizer, the preservability thereof is seriously deteriorated, and it is said that any small amount of replenishment cannot be made even if a replenishing solution is prepared. The same may be said of a fixing solution and a stabilizing solution.
Besides the above-mentioned problems, a replenishing solution has been getting more concentrated while low and rapid replenishing techniques have been progressed and, therefore, the recent replenishing solutions have been usually concentrated up to the limit of a solubility.
From the practical viewpoints, the above-mentioned facts also induce many problems that the preservability of a replenishing solution is deteriorated and, moreover, crystals are deposited.
On the other hand, separate from the method in which a replenishing solution is prepared by making use of such a concentrated kit or powdered chemical as mentioned above, there is also a known method for directly replenishing a concentrated kit.
The above-mentioned method is to replenish a concentrated kit directly to a processing tank by making use of a supplying means such as a bellows pump so that the ineffectiveness of a dissolving operation can be improved and, at the same time, the method is to replenish a specific amount of water independently. In this method, it is no doubt that a work for preparing a solution can be eliminated, as compared to the method for preparing a replenishing solution of the above-mentioned concentrated kit or powder,-or that a preservation problems can be eliminated because any replenishing solution is not prepared.
However, the above-mentioned method has also many problems. For example, a problem is that a tank for a concentrated kit and a pump for serving as a supplying means are additionally required to supply the concentrated kit, so that an automatic processor has to be made larger in size. Taking a CPK-2-20 that is a color paper processing solution into consideration, for example, the concentrated kit for a replenishing solution for color development is comprised of 3 parts, the concentrated kit for a replenishing solution for bleach-fixation is comprised of 3 parts and the concentrated kit for replenishing solution for stabilization is comprised of 2 parts. When supplying the parts of every kit, 8 tanks for the concentrated kits and 8 pumps for supplying them are necessarily required. In the case of a conventional replenishment system, it could be enough to provide the tanks and pumps for every replenishing solution and, therefore, a replenishment can be performed by providing only 3 each of tanks and pumps. As mentioned above, even when taking the case of supplying the concentrated kits only into consideration, not only many tanks and pumps but also a pump for controlling an amount of water to be supplied are respectively required for this method as compared to the conventional methods. Further there is such a disadvantage that plural solutions can hardly be spilled precisely at the same time from a bellows pump, so that an unbalance may be produced between the amounts of each component, because the accuracy of the bellows pump is not so high.
Further, crystals are liable to deposit around the orifice of a replenishing nozzle because the concentrated kits are in the form of a concentrated solution. Therefore, the maintenance of a replenishing nozzle is troublesome. Still further, when replenishing a concentrated solution, the replenishment accuracy is liable to become seriously erratic because the bellows pump is not very high in supplying accuracy. Resultingly, there raises such a problem that the photographic characteristics are seriously fluctuated. Besides the above, there is another problem that the amounts of waste plastic containers are as same as in the case of the conventional system, even if the system for supplying a concentrated kit is used.
Separate from the above-described methods, there are some proposals for improving the chemical stability of a replenishing solution.
For example, Japanese Patent Publication Open to Public Inspection (hereinafter referred to as JP OPI Publication) No. 58-11032/1983 discloses a technique for filling a development component into a microcapsule. JP OPI Publication No. 51-61837/1976 discloses a photographic tablet containing a decaying agent. And, JP OPI Publication Nos. 2-109042/1990, 2-109043/1990, 3-39735/1991 and 3-39739/1991 discloses each a method for making use of a granulated photographic processing chemical having a certain average particle size.
The photographic tablet containing a decaying agent described in JP OPI Publication No. 51-61837/1976 is simply proposed to be a tablet readily dissolvable with water. This proposal can suggest nothing of such an idea of this invention that a solid processing chemical is directly dissolved in a processing tank.
JP OPI Publication No. 2-109042/1991 describes of a granulated photographic processing chemical having a certain average particle size.
However, the above-mentioned patent publications do not propose any compact-sized automatic processor from which a replenishing solution dissolving work can be eliminated to satisfactorily simplify a workability so that a stable photographic characteristics can be obtained and a replenishing tank can also be eliminated.
On the other hand, for the methods from which a preliminary dissolving work is eliminated, JP OPI Publication No. 3-11344/1991 discloses a technique in which a paste-formed part chemical is extruded in an amount corresponding to a mixed ratios of the part chemicals from each of unit containers and the extruded part chemical is controlled and supplied precisely by diluting it to have a specific concentration. According to this method, it is no doubt that the dissolving works can be reduced or eliminated, however, the paste-formed part chemical may lack in stability because it contains a solvent and a series of the extrusion in a constant amount can hardly be performed for a long time and, further, a nozzle is liable to be clogged if not frequently used, so that the photographic characteristics can hardly be maintained constantly. In addition, it is required to use a container for putting the paste therein and, in this case, a flexible and hardly damageable material is required to be used, that is, however, a compounded material generally incapable of being recycled, so that this kind of material is not preferable from the viewpoint of environmental protection. In particular, a paste-formed chemical is often made into a paste form by making use of an organic solvent and it has, therefore, been known that the preservability thereof is not much acceptable.
Japanese Utility Model Publication Open to Public Inspection No. 1-85732/1989 discloses an automatic processor having a means for adding a tablet type microbiocide to a stabilizing solution. The control of adding the microbiocide is not necessary, because the microbiocide itself does not raise any problem even if many of them are added. Therefore, this disclosure does neither suggest any idea of a means for controlling the replenishment of a processing solution, nor suggest any of the means to be inevitable, because the microbiocide has the purpose of keeping the solution itself antiseptic.
WO 91-07698 and WO 91-07699 disclose each a method for adding CD-3 or CD-4 in the form of a solid and the other components as an activator in the form of a liquid. These patents are each concerned in a regeneration and particularly in an invention of a low replenishment unlimitedly close to a so-called no-overflow replenishment, that is, a method in which bromide ion and chloride ion are made adsorbed to be removed from a developing solution by making use of an ion-exchange resin and then for adding an insufficient component such as an alkalizing activator and a solid-formed or small amount of a concentrated color developing agent, so as to add the components without increasing any volume.
JP OPI Publication No. 4-213454/1992 describes that a powdered processing chemical is directly added to the auxiliary tank of an automatic processor. However, this patent publication does not describe anything of the time for dissolving the powdered processing chemical, nor is the method for adding a processing chemical to a subject light-sensitive material described. In the case of a conventional type liquid-formed replenishing solution system, the liquid-formed replenishing solution is used for keeping a processing solution constant in a processing tank. For example, the liquid-formed replenishing solution has played a role for diluting an accumulated component eluted out of a subject light-sensitive material, or it has mainly played a role for replenishing a components consumed with a subject light-sensitive material. In contrast to the above, in the case of a system for directly adding a solid-formed processing chemical to a processing solution reserved in a processing tank, the liquid-formed replenishing solution is to play a role for replenishing a consumed component, and the role for diluting an accumulated component is to be played by a replenished water.
However, a solid-formed processing chemical is to be dissolved in a processing tank. It is normally considered that the shorter a dissolving time is the better. If a dissolving time is too short when directly adding a solid-formed processing chemical to a processing solution, a component subject to consumption becomes in an excessively added state for a moment and, therefore, the balance between the consumption and supply thereof is lost and, resultingly, a processability is fluctuated, so that a problem is raised to lack a stability. For a measure to counter this problem, it may be considered to reduce an amount of a solid-formed processing chemical to be added and then to increase the frequency of adding it. In this case, there raises such a problem that an increased load is applied to a solid-formed processing chemical supplying unit so as to shorten the lifetime thereof or that a tablet type chemical or a solid-formed processing chemical separately weighed in advance and individually packed as an adding unit are each to have many packing units.
If a dissolving time is-made much longer, the supply of a solid-formed chemical becomes excessive in relation to the time of dissolving it in a processing tank so that the insoluble matter of the solid-formed processing chemical is accumulated in the processing tank. Therefore, a problem of producing a precipitate in the processing tank is raised.
The present inventors have repeated to try many experiments of the methods for directly dissolving a solid-formed processing chemical in a processing tank and finally discovered the above-described points at issue.